EP1695943A2 - Verfahren zur Wiedergewinnung von Produkten des Nassoxidationsverfahren um Keramikmaterial zu produzieren - Google Patents

Verfahren zur Wiedergewinnung von Produkten des Nassoxidationsverfahren um Keramikmaterial zu produzieren Download PDF

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Publication number
EP1695943A2
EP1695943A2 EP06003680A EP06003680A EP1695943A2 EP 1695943 A2 EP1695943 A2 EP 1695943A2 EP 06003680 A EP06003680 A EP 06003680A EP 06003680 A EP06003680 A EP 06003680A EP 1695943 A2 EP1695943 A2 EP 1695943A2
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EP
European Patent Office
Prior art keywords
sludge
pressure
component
ranging
bars
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06003680A
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English (en)
French (fr)
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EP1695943A3 (de
Inventor
Franco Sardelli
Massimiliano Valle
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3v Matex Spa
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3v Matex Spa
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Publication of EP1695943A2 publication Critical patent/EP1695943A2/de
Publication of EP1695943A3 publication Critical patent/EP1695943A3/de
Withdrawn legal-status Critical Current

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
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Definitions

  • the present invention relates to a method for converting sludge, particularly excess sludge from plants for biological purification of civil and industrial wastewater.
  • Excess sludge is characterized by the content of suspended solids (hereinafter SS) and by the weight ratio (volatile suspended solids)/(total suspended solids), hereinafter referenced as VSS/SS, where the expression "volatile suspended solids” designates the fraction of SS which bums or is vaporized by heating in air the total suspended solids at 600°C and is constituted substantially by oxidizable organic substances. The remaining part of the sludge is substantially inorganic.
  • SS suspended solids
  • VSS/SS total suspended solids
  • excess sludge is extracted from the biological plant with a solids concentration ranging on average from 0.5% to 1% by weight and is thickened, before being removed, to approximately 2.5-3.5% by weight. If not specified, the concentrations of SS and VSS are understood to be by weight on the total weight of the sludge.
  • the sludge After its extraction, the sludge is conventionally subjected to successive treatments, which include filtration, centrifugation, and reduction in volume by means of a suitable technique, such as wet oxidation, anaerobic fermentation, sludge heating, drying and incineration.
  • a suitable technique such as wet oxidation, anaerobic fermentation, sludge heating, drying and incineration.
  • the sludge is then sent to disposal, for example in agriculture or landfills.
  • Disposal in agriculture allows to recover the humifying and fertilizing potential of the sludge.
  • severe legal constraints (reference should be made in this regard to directive 86/278/EEC and to Government Legislative Decree no. 99 dated 27 January 1992) make agricultural disposal unfeasible for most industrial sludge, which has an excessively high chemical and bacteriological polluting potential.
  • the aim of the present invention is therefore to provide a new method for treating sludge, preferably excess sludge originating from plants for biological purification of civil and industrial wastewater, which overcomes the drawbacks of the background art.
  • An object is to provide a treatment as described above which does not end with conventional disposal of the products of such treatment.
  • Another object is to provide a method as described above which stabilizes and sanitizes a sludge.
  • Another object is to provide a method as described above which is economically advantageous and less harmful to the environment than the background art.
  • Still another object is to provide a method as described above which produces products which are superior to their currently commercially available equivalents.
  • a method for converting and enhancing the value of a biological sludge having an initial SS content of less than 15% by weight on the total weight of the sludge, preferably an excess sludge originating from plants for biological purification of civil and industrial wastewater comprising the steps of:
  • an apparatus for carrying out a method for converting and enhancing the value of biological sludge having an initial SS content of less than 15% by weight on the total weight of the sludge which comprises:
  • the invention relates to a method for treating industrial sludge, such as excess sludge, which comprises its wet oxidation, the recovery of the component of the effluent which contains the solids of the oxidation step, and the value enhancement of the residue by subjecting it advantageously first to a formation step, preferably with a combination of atomization and granulation, and then by firing it so as to obtain a ceramic material which has new physical characteristics.
  • the invention in another aspect, relates to an apparatus for carrying out the method described above.
  • the apparatus comprises means for performing the wet oxidation of sludge, means for recovering the component of the effluent which contains the solids, and means for forming and firing the recovered solid residue.
  • the invention relates to an intermediate ceramic material, such as a granulate, which can be obtained with the method described above and can be used to produce finished ceramic materials.
  • the invention relates to finished ceramic materials produced starting from intermediate materials and preferably from a granulate.
  • a first aspect of the invention relates to a method for treating and enhancing the value of industrial sludge having a pumpable consistency and therefore an SS content of less than 15% by weight on the total weight of the sludge.
  • the sludge is excess sludge which originates from plants for biological purification of civil and industrial wastewater.
  • a part of the component which contains the liquids also can be recycled advantageously in the wet oxidation apparatus.
  • a method for wet oxidation of sludge such as excess sludge, if continued until the substrate is inertized, is adapted to convert the sludge into a stabilized mineral residue.
  • stabilized is used to designate a residue without putrescible organic substances and without a bacterial load, which therefore remains substantially stable over time.
  • said inertized mineral residue is an unexpectedly advantageous raw material for use in the production of innovative ceramic materials, such as for example dense and light calcined clay for various fields of application, such as refractories, bonding agents for the building sector, concretes, sanitary fixtures, bricks and tiles.
  • the wet oxidation step must continue long enough to achieve inertization of the sludge.
  • inertization is used to mean that the organic component of the initial sludge is mineralized, i.e., essentially eliminated, because it is mostly oxidized to water and carbon dioxide, and is rendered water-soluble in the remaining fraction and therefore eliminated with the liquid phase that contains it. Inertization entails a great reduction of the organic and bacterial load of the sludge, allowing its stabilization and sanitizing.
  • the VSS content in the effluent is reduced by at least 75% with respect to the initial value, preferably at least 90%, more preferably by a percentage ranging from 90% to 100%.
  • the steps of wet oxidation and recovery of the solid component can be performed in a known manner and in conventional devices, in view of the need for the sludge to be treatable (i.e., pumpable) and for the reduction in VSS content to be equal to at least 75% of the initial value.
  • the steps i) of wet oxidation and ii) of recovery of the solid component occur according to the method, and with an apparatus, as described in a co-pending application entitled "Method and apparatus for wet oxidation of sludge", filed by 3V GREEN EAGLE S.p.A..
  • the step i) of wet oxidation of sludge with an SS content of less than 15% by weight on the total weight of the sludge comprises at least one step of increasing the temperature of the sludge by using at least one injection of high-pressure steam.
  • high-pressure steam is used to designate steam at a pressure ranging from 18 to 85 bars and in any case higher than the pressure at which wet oxidation occurs.
  • the wet oxidation step comprises the steps of:
  • step ii In order to recover a solid residue (step ii), after steps a)-d) of oxidation, the following additional step is performed:
  • step e after recovering from step e) the component which contains the solids and before sending it to value enhancement, the following additional step is performed at least once:
  • the SS content of the treated sludge ranges from 2% to 15% by weight on the total weight of the sludge.
  • the sludge to be treated has an initial SS content of more than 15% by weight on the total weight of the sludge, it is possible to perform an additional step a') of diluting the sludge with water, wherein said dilution step must be performed as the first step.
  • the sludge is to be oxidized by applying less heat, it is possible to increase the COD of the sludge by performing a step a") of concentrating the sludge, which must be performed before the other steps, optionally with the aid of flocculants and/or polyelectrolytes.
  • flocculants and "polyelectrolytes” designate usually polymeric substances which are capable of producing the coagulation, flocculation and settling of the sludge.
  • flocculants are inorganic flocculants selected among iron chloride and sulphate, aluminum chloride, polychloride and sulphate, and mixtures thereof.
  • polyelectrolytes are organic polyelectrolytes selected among polyols, polyesters, polyethers, polyacrylates and/or polyacrylamides, optionally substituted, and mixtures thereof.
  • the temperature of the sludge is raised advantageously to a value ranging from 180°C to 260°C, a temperature which is the conventional one for oxidation to occur in industrially useful times.
  • the step of preheating the sludge, if performed, is also possible and preferable for the step of preheating the sludge, if performed, to occur by means of one or more injections of low-pressure steam instead of by means of the conventional use of heat exchangers.
  • low-pressure steam designates steam at a pressure ranging advantageously from 0.1 bars to 15 bars, a temperature ranging from 105°C to 200°C, which as explained below can be injected in different points according to the requirements but in any case necessarily upstream of the pump which feeds the sludge to the reactor.
  • high-pressure steam designates steam at a pressure which is higher than the operating pressure of the oxidation reactor and ranges from 18 to 85 bars, advantageously from 30 bars to 55 bars, and a temperature ranging from 210°C to 300°C, preferably ranging from 235°C to 270°C.
  • the solid and inert component of the effluent of the oxidation of the sludge is a powder which has a fine and uniform particle size distribution. Chemical and particle size uniformity make the mineral component extremely suitable for use as raw material in further industrial processes and in particular for the production of ceramic materials.
  • the inorganic stabilized solid fraction is formed and converted by heat into ceramic materials.
  • this step it is possible to provide successfully, for example, granular and monolithic lightweight materials to be intended for technical uses in the building sector and specifically in the field of refractory materials.
  • composition of a typical solid residue recovered from wet oxidation of an excess sludge has been found to be as follows: moisture content at 105°C, 40-50%; ignition loss at 600°C, 20-30%; analysis on the residue at 600°C: CaO 15-50%, P 2 O 5 10-30%, MgO 0-10%, SiO 2 0-8%, Fe 2 O 3 0-6%, ZnO 0-2%, Al 2 O 3 0-2%, Cr 2 O 3 0-0.3%, MnO 0-0.3%, others 0-1%, where the percentages are by weight.
  • the inert residue was found to be constituted substantially by calcium phosphate typically organized into an apatite structure Ca 5 (PO 4 ) 3 .
  • Other chemical elements are optionally present depending on the initial composition of the sludge, but other phases different from apatite are non-characterizing, since they occur occasionally and in small amounts.
  • An amorphous phase has been found to be the collector of the chemical elements which find no place in the apatite structure, while a small percentage of VSS, at most 30% by weight on the total weight of the residue, is generally still present.
  • the remaining organic portion is not chemically identical to the initial portion, since the oxidation treatment has made it stable, i.e., imputrescible and with no bacterial load.
  • step iii) of value enhancement which leads to ceramic products, can be defined schematically and in a non-limiting way by means of the following items:
  • step iii) comprises the steps of:
  • ceramic material designates a fired and formed material, either a finished ceramic article or preferably an intermediate ceramic material such as a granulate, which in turn can be used to provide finished ceramic articles, concretes and bonding agents.
  • step e) of preparing the mix comprises the steps of:
  • the steps of weighing, milling and mixing can occur by way of known techniques.
  • the dry ingredients are mixed. If one of the ingredients is added in the form of a liquid, it is advantageous to introduce it at a later time with respect to dry powders, together with any water needed to reach the consistency of the mix which is most sought for the formation.
  • the optional ingredients added to the residue inertized by sludge oxidation are selected among the ones typically used in the field of ceramics (including technical ceramics), in the building and concrete sector, as well as among other waste materials of different origin (including organic ones). These optional ingredients are selected, for example, from the group which comprises:
  • the formation step occurs so as to give the mixture a spherical shape.
  • formation which is designed to develop lightened materials, is selected among techniques for atomization, granulation or a combination of these two techniques.
  • Atomization is a technique which is known in the field of the preparation of ceramic powders to be molded by pressing (technical ceramics and tiles) and allows to form highly spherical granules which are hollow internally, usually with a goblet-like hole for connection to the outside.
  • the atomization technique comprises preparing the mix as above so that it has the consistency of a slurry in which the solid portion ranges from 40% to 70% by weight on the weight of liquid fraction, and atomizing the mix within a vertical dryer so as to dry it rapidly.
  • the variables on which one can work in order to change the characteristics of the atomized substance are correlated to the rheologic characteristics of the suspension (viscosity, flowability, amount of suspended solid) and to plant parameters such as the dimensions of the dryer, the drying temperature, the size and quantity of the atomizing nozzles.
  • the person skilled in the art will know how to easily modify these parameters so as to obtain the intended result.
  • Atomization is particularly convenient for producing small granules, particularly with an average diameter of less than 500 microns.
  • One of the fundamental characteristics of the atomized substance, in addition to the flowability which derives from the spherical shape of the particles that constitute it, is high compressibility.
  • Granulation comprises aggregating the material by agitating the ingredients in the form of dry powders which are gradually wet.
  • the granules that form have a more or less conspicuous roundness, depending on parameters such as the mixing times or the ratio between powder size and formed granule size.
  • Granulation provides solid spheres and, differently from atomization, is preferably adapted to provide less compressible granules which have a diameter of more than 500 microns.
  • the formation technique comprises the combination of the techniques of atomization and granulation in this order.
  • This combination provides for the production of a first granule by atomization, which is then subjected to granulation.
  • internally hollow spherical granules with a diameter of less than 500 microns but without the presence of the surface hole have been formed in this manner.
  • additives which are typical of the field and are known to contribute to the physical properties of the formed ceramic product.
  • additives comprise for example thickening agents, bonding agents, foaming agents and mixtures thereof. The quantities of these ingredients can be determined by the person skilled in the art by means of routine experiments.
  • the spheres are fired by applying temperature gradients and holding times which can be determined easily by a person skilled in the art and differ depending on the products to be obtained, on the raw materials and on the initial particle size distribution. Firing occurs conventionally in rotary kilns at maximum temperatures generally ranging from 950°C to 1500°C.
  • the resulting spherical products are new and advantageous, since after firing they have a compressive strength of 30 to 50 MPa and a density of 0.3 to 0.5 g/cm 3 .
  • the materials that have the highest ratios of mechanical compressive strength/density can be provided with a particle size of less than 500 microns preferably by combining the atomization and granulation techniques and with a grain size of more than 500 microns preferably by granulation.
  • the ceramic material obtained with the combination of atomization and granulation has the appearance of a lightened granulate, constituted by a combination of materials having a preset composition, with a highly regular spherical shape, with a diameter of preferably less than 4 mm, more preferably ranging from 100 to 500 microns, with a density of less than 1 g/cm 3 , preferably ranging from 0.1 to 0.5 g/cm 3 , and closed or open porosity, which in any case can be modified according to the technical requirements.
  • the advantages of such a granulate will become better apparent in the examples that follow.
  • the invention in another aspect, relates to an apparatus for carrying out a method which leads from industrial sludge to a ceramic granulate.
  • This apparatus is characterized in that it comprises means for performing the wet oxidation of sludge, means for recovering the component of the sludge oxidation product which contains the solids, means for formulating and mixing the recovered component, and means for forming and firing the component so as to obtain a ceramic material.
  • Means for milling the component recovered from wet oxidation are also optionally provided.
  • the apparatus for performing the wet oxidation of sludge (step i) and the recovery of the component which contains the solids (step ii) comprises at least one oxidation reactor, means for pressurizing said sludge and feeding it to said reactor, and means for adding oxygen inside said apparatus, and is characterized in that it comprises means for injecting steam at a pressure ranging from 18 to 85 bars in at least one point inside it and at least one settling tank which is arranged downstream of said reactor.
  • the presence of at least one settling tank is required in order to have means for separating the component of the effluent which contains the liquids from the component which contains the solids, which will be sent to enhancement.
  • the means for injecting steam comprise nozzles and at least one high-pressure steam generator (such as an evaporator).
  • the nozzles for injecting the high-pressure steam are arranged advantageously at at least one point selected between said at least one reactor and the means (pipes) for feeding the sludge under pressure to said reactor.
  • the apparatus further comprises at least one preheating chamber, which is arranged upstream of said at least one reactor and is connected thereto.
  • the apparatus further comprises at least one expansion chamber, which is arranged downstream of the at least one reactor.
  • the settling tank is arranged downstream of said at least one expansion chamber, if said chamber is present.
  • the apparatus since it is important for the solid residue to be enhanced to contain the lowest possible amount of organic material, it is highly preferred for the apparatus to further comprise also at least one scrubber arranged downstream of said settling tank.
  • this embodiment of the apparatus further comprises means for injecting low-pressure steam, which are arranged upstream of the means (pump) for pressurizing the sludge to be oxidized.
  • the means for injecting low-pressure steam can be nozzles arranged at the at least one preheating chamber or arranged at means which feed said sludge to said preheating chamber.
  • the means for forming the mix are at least one among the following:
  • the means for optionally milling the solid residue recovered from wet oxidation, the means for formulating and mixing the milled solid residue with any optional ingredients, and the means for firing the formed residue are of a conventional type.
  • a wet oxidation apparatus in which the excess sludge produced by the biological plant for purifying the wastewater of a chemical factory and various aqueous waste of external origin are treated with pure oxygen.
  • reaction parameters are: temperature: 220-240°C, pressure: 40-50 bars.
  • the plant operates with a reactor having an inside diameter of approximately 0.6 m and a height of approximately 5 m.
  • the reactor which is kept at a pressure of 45 bars, is fed with 870 1/h of sludge as described above, preheated to 97°C by introducing in the preheating tank 130 kg/h of low-pressure steam (recovered from the atmospheric flash of the effluent of the reactor). 280 kg/h of steam, saturated at 55 bars, and oxygen in a stoichiometric quantity (approximately 30 kg/h) are also introduced in the reactor.
  • the temperature of the reactor (head) rises to 240°C (which is also the output temperature from the reactor).
  • the effluent of the reactor undergoes a first flash at a pressure of approximately 16 bars and 180°C, which allows to separate the reaction gases (carbon dioxide and oxygen) and the excess steam that is produced, and then undergoes a second flash at a pressure which is slightly higher than the atmospheric pressure (0.1-0.3 bars), producing the 130 kg/h of steam required to preheat the feed.
  • the resulting conversion is higher than 65%.
  • the reduction in total suspended solids is over 83% of the initial amount and the reduction in volatile suspended solids is approximately 98% of the initial amount.
  • the resulting slurry is accumulated on the bottom of the settling tank and is transferred every 4-6 hours into a conventional conical-cylindrical mixer-settler, where it is scrubbed repeatedly by mixing, subsequent settling and discharge of the supernatant, with alkaline solutions and neutral water until the mother liquor and the organic substances contained therein are removed completely.
  • the discharged scrubbing wastewater is recycled to the biological plant in order to be purified of the organic substance content.
  • the scrubbed slurry is filtered on a filter press, obtaining panels with a dry substance content of approximately 50%.
  • the resulting panels have the following characteristics: Residue at 105°C (dry substance) 48% Residue at 600°C 43.2% Residue at 600°C (on dry substance) 89.6%
  • the panels are then dried in a drum dryer.
  • a wet oxidation plant in which pure oxygen is used to treat the excess sludge produced by the plant for biological purification of the wastewater of a chemical factory and various aqueous waste of external origin.
  • the sludge, before being fed to the wet oxidation, is thickened, by means of a sifter and with the addition of small amounts of polyelectrolyte, in order to bring the concentration of the suspended solids to approximately 6%.
  • reaction parameters are: temperature: 220-240°C, pressure: 40-50 bars.
  • the plant operates with a reactor having an inside diameter of approximately 0.6 m and a height of approximately 5 m.
  • the reactor kept at a pressure of 45 bars, is fed with 870 1/h of sludge as defined above, preheated to 97°C by introducing in the preheating tank 130 kg/h of low-pressure steam (recovered from the atmospheric flash of the effluent of the reactor). 200 kg/h of saturated steam at 55 bars and oxygen in a stoichiometric quantity (approximately 30 kg/h) are also introduced in the reactor.
  • the temperature of the reactor rises to 240°C (which is also the output temperature from the reactor).
  • the effluent of the reactor undergoes a first flash at a pressure of approximately 16 bars and 180°C, which allows to separate the reaction gases (carbon dioxide and oxygen) and the excess generated steam, and then undergoes a second flash, at a pressure which is slightly higher than atmospheric pressure (0.1-0.3 bars), which produces 130 kg/h of steam needed to preheat the feed.
  • SS 0.43% 4300 mg/l VSS/SS 0.102 COD: 11600 mg/l
  • the resulting conversion (reduction of COD) is higher than 65%.
  • the reduction in total suspended solids is higher than 83%, and the reduction in volatile suspended solids is approximately 98%.
  • the resulting slurry accumulates on the bottom of the settling tank and is transferred every 4-6 hours into a conventional conical-cylindrical mixer-settler, where it is scrubbed repeatedly by mixing, subsequent settling and discharge of the supernatant with alkaline solutions and water until the mother liquor is removed completely together with the organic substances contained therein.
  • the discharged scrubbing wastewater is recycled to the biological plant to be purified of the organic substance content.
  • the scrubbed slurry is filtered on a filter press, obtaining panels with a dry substance content of approximately 50%.
  • the resulting panels have the following characteristics: Residue at 105°C (dry substance) 52% Residue at 600°C 46.7% Residue at 600°C (on dry substance) 89.8%
  • the panels are then dried in a drum dryer.
  • This example describes the advantages arising from the use of the mineral residue of wet oxidation of excess sludge in devising ceramic mixes adapted to provide ceramic products applied in the field of refractory materials.
  • Table 1 lists the composition of some ceramic raw materials, such as gypsum, calcite and wollastonite, used typically to add calcium to ceramic mixes.
  • these compositions are compared with apatite, which as mentioned is the fundamental component, and in some cases the only component, of the inorganic material obtained from the wet oxidation of an inertization sludge. It can be appreciated that the mineral residue according to the invention is a valid replacement of other ingredients which add calcium.
  • the mineral residue replaces, in the formulation, other calcium-adding components, among which the most frequently used are, as mentioned, gypsum (CaSO 4 ⁇ 2H 2 O) and calcite (CaCO 3 ).
  • composition of these mixes which are particular and common in the field of refractory ceramic materials, are given in Table 2.
  • Table 2 Chemical composition of mixes Si 2 O% Al 2 O 3 % CaO% 1) anorthite CaAl 2 Si 2 O 8 43.3 36.5 20.2 2) 40% alumina + 60% anorthite 26 61.9 12.1 3a) 30% mullite + 70% anorthite 36.9 49 14.1 3b) 50% mullite + 50% anorthite 32.6 57.3 10.1 3c) 70% mullite + 30% anorthite 28.2 65.7 6.1
  • the formulation (1) which is apparently the simplest and starts from the pure oxides is also the one that requires the greatest use of energy to produce the crystallization reactions of the phases that constitute the ceramic material. Moreover, the absence of clay forces the use of additives adapted to make the ceramic mix plastic and strong when unfired.
  • Mixes 2 and 3 instead resort to kaolinite clay as a vehicle for introducing silicon and alumina and to sulphates and/or carbonates as a vehicle for introducing calcium.
  • kaolinite clay as a vehicle for introducing silicon and alumina
  • sulphates and/or carbonates as a vehicle for introducing calcium.
  • This example describes a method for forming a ceramic mix prepared with the inorganic residue of an oxidized excess sludge.
  • the operations may be different depending on the goal to be achieved and on the selected technique. It is possible to use all the formation techniques classically used, such as pouring, drawing, pressing, atomization and granulation. For the production, here preferred, of spherical granulates with a size ranging from 0.1 to 2 mm (100-2000 microns), it is preferable to use two techniques: atomization and/or granulation.
  • Spherical granulates with anorthite composition having a size of 100-300, 200-500, 500-1000, 1000-2000, 2000-4000 microns and with densities of 0.2-0.5 g/cm 3 have been provided by using the anorthite mixture described in Example 3. These spherical granulate have been formed by atomization combined with granulation for particle sizes up to 1000 microns and by granulation for particle sizes greater than 1000 microns.
  • pre-fired granulates described above which have the significant advantage of having an identical anorthite composition with respect to the matrix in which they are inserted, produces for example the advantage of using lower amounts of gypsum and water to form the articles by pouring, and consequently provides a significant acceleration of production times.
  • the method according to the invention achieves the intended aim and objects, since it allows to eliminate a waste which up to now was considered as inevitably meant for disposal, with severe repercussions on costs and on the environment, by combining with a step of wet oxidation of the sludge a step for preparing ceramic matrices which enhances the value of the non-oxidizable mineral residue, making it return to the industrial cycle.
EP06003680A 2005-02-28 2006-02-23 Verfahren zur Wiedergewinnung von Produkten des Nassoxidationsverfahren um Keramikmaterial zu produzieren Withdrawn EP1695943A3 (de)

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CN113896562A (zh) * 2021-09-27 2022-01-07 同济大学 一种利用污泥制备多孔陶粒的方法及得到的多孔陶粒
CN115286362A (zh) * 2022-08-09 2022-11-04 湖南富强特种陶瓷制造有限公司 一种可自然降解陶瓷材料及其制备方法

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